EP0103106B1 - Utilisation d'un polymère de 1,3-butadiène à bas poids moléculaire contenant des groupes amine comme stabilisant de matières plastiques - Google Patents

Utilisation d'un polymère de 1,3-butadiène à bas poids moléculaire contenant des groupes amine comme stabilisant de matières plastiques Download PDF

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Publication number
EP0103106B1
EP0103106B1 EP83106914A EP83106914A EP0103106B1 EP 0103106 B1 EP0103106 B1 EP 0103106B1 EP 83106914 A EP83106914 A EP 83106914A EP 83106914 A EP83106914 A EP 83106914A EP 0103106 B1 EP0103106 B1 EP 0103106B1
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EP
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Prior art keywords
stabilizer
plastics
iodine
polybutadiene
molecular weight
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EP83106914A
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German (de)
English (en)
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EP0103106A1 (fr
Inventor
Alfred Dr. Konietzny
Hans-Dieter Dr. Zagefka
Konrad Dr. Rombusch
Hanns-Jörg Dr. Bax
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Huels AG
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Huels AG
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C19/00—Chemical modification of rubber
    • C08C19/30—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule
    • C08C19/34—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule reacting with oxygen or oxygen-containing groups
    • C08C19/40—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule reacting with oxygen or oxygen-containing groups with epoxy radicals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation

Definitions

  • the invention relates to the use of a low molecular weight 1,3-butadiene polymer carrying amino groups as a stabilizing agent for molded or unshaped plastics.
  • the higher molecular weight, in particular polymeric derivatives of sterically hindered piperidine derivatives that have become known have the disadvantage, as light stabilizers for plastics, that they are either not sufficiently effective in the plastic to be finished and / or are not compatible with them.
  • EP-A-1 803 copolymers are known from butadiene and piperidine derivatives, which carboxylic acid esters or. Contain carboxamide groups. Such substances are extremely sensitive to hydrolysis because of the ester or amide grouping and also cannot be used sufficiently as stabilizers because of the high degree of unsaturated double bonds.
  • the object was therefore to provide higher molecular weight, in particular polymeric tetramethylpiperidine derivatives which are well compatible with the plastics and stabilize them very well.
  • the stabilizing effect should be permanent, i.e. H. the stabilizers are said to be practically non-volatile and non-extractable or to have practically no tendency to migrate.
  • the stabilizing agents of the invention are particularly good light stabilizers.
  • the object is achieved by using a low molecular weight 1,3-butadiene polymer bearing amino groups as claimed in the claims as a stabilizing agent for molded or unshaped plastics.
  • This 1,3-butadiene polymer is obtained by reacting an epoxidized polybutadiene with an epoxy content of 2 to 10% by mass oxygen (according to DIN 16 945) with a substituted piperidine of the general formula in which R can be the same or different types of alkyl radicals with 1 to 3 carbon atoms, up to a content of 0.3 m tetraalkyl-piperidine / 100 g of reaction product, the base polybutadiene having a molecular weight (Mn) of 500 to 6,000, an iodine number of at least 200 and has a content of double bonds in trans structure of at most 40%.
  • Mn molecular weight
  • the epoxy content of the epoxidized polybutadiene is advantageously 4 to 8% by mass.
  • the double bonds of the base polybutadiene can have been hydrogenated up to an iodine number of at most 10.
  • Suitable as the basic polybutadiene for the stabilizing agent is one which is composed of at least 70 mol% of 1,3-butadiene.
  • Copolymerizable 1,3-diolefins such as isoprene and 1,3-pentadiene, are suitable as comonomers.
  • Copolymerizable, ⁇ -unsaturated monoolefins, such as styrene, can also be used as comonomers. However, they are less preferred than comonomers.
  • the copolymers are preferably composed of at least 90 mol% of 1,3-butadiene and at most 10 mol% of the comonomers.
  • Homopolybutadienes are very particularly preferred.
  • the base polymers have a molecular weight (Mn) of 500 to 6,000, preferably 800 to 3,000 (determined by vapor pressure osmometry), and an iodine number of at least 200, preferably at least 300 g iodine / 100 g.
  • the 1,3-butadiene polymers containing epoxy groups can, for. B. from butadiene (co) polymers, as exemplified in DE-PSS 11 86 631, 12 12 302, 12 41 119.12 51 537, 12 92 853, 20 29 416, 21 22 956 and DE-OS 23 61 782 are described, prepared by epoxidation, the epoxidation being able to be carried out in a manner known per se, for example as described in DE-PS 28 38 930, column 7, last paragraph, wherein vinyl groups may also be epoxidized.
  • butadiene (co) polymers as exemplified in DE-PSS 11 86 631, 12 12 302, 12 41 119.12 51 537, 12 92 853, 20 29 416, 21 22 956 and DE-OS 23 61 782 are described, prepared by epoxidation, the epoxidation being able to be carried out in a manner known per se, for example as described in DE-PS 28
  • the polymer content of titratable epoxy oxygen (DIN 16 945) is 2 to 10% by mass, preferably 4 to 8 mass%. In the homo- or copolymers containing epoxy groups, at most 40% of the olefinic double bonds are present in a trans structure.
  • the epoxidized butadiene polymer is isolated in a manner known per se, e.g. B. analogous to DE-PS 28 38 930, reacted in the heat with the sterically hindered piperidine derivative and then optionally catalytically, partially or completely in a manner known per se, d. H. up to an iodine number of 10 (g iodine / 100 g), hydrogenated.
  • Examples of a base polymer are (a) a polybutadiene with a molecular weight of 1,700, an iodine number of 450 (g iodine / 100 g), a cis / trans / vinyl ratio of 72/27/1; (b) a polybutadiene of molecular weight 1,050, the iodine number 390 (g iodine / 100 g), the cis / trans / vinyl ratio of 0/13/87; (c) a polybutadiene of molecular weight 1,300, iodine number 390 (g iodine / 100 g), cis / trans / vinyl ratio of 20/30/50; (d) a polybutadiene of molecular weight 1,300, iodine number 440 (g iodine / 100 g), the cis / trans / vinyl ratio of 49/14/37; (e) a polybutadiene with
  • the stabilizers according to the invention are used in the polymers in a concentration of 0.01 to 2.0, preferably 0.1 to 1.0, in particular 0.2 to 0.5,% by mass, based on the plastic to be stabilized.
  • Suitable plastics are homopolymers and copolymers of olefins or diolefins, polyisoprene, polybutene, polypropylene, low and high density polyethylene, polybutadiene or saturated or unsaturated ethylene-propylene copolymers, ethylene-butene copolymers, ethylene-vinyl acetate copolymers, butadiene-styrene Copolymers, butadiene-styrene-acrylonitrile copolymers, furthermore homopolymers and copolymers of styrene or its homologues, such as a-methylstyrene or p-methylstyrene, e.g. B.
  • impact-resistant polystyrene types such as graft polymers of styrene with elastomers or mixtures of homo-, co- or
  • plastics containing carbonamide groups such as a) polyamides, e.g. B. homopolyamides, as they are in the usual way from lactams with more than 5 carbon atoms in the ring or from the corresponding w-amino acids, such as caprolactam, capryllactam, laurolactam, undecyllactam, oenanthlactam, or from ⁇ , o-diamines and ⁇ , o- Dicarboxylic acids with more than 3 carbon atoms between the functional groups, such as, for example, tetramethylene diamine, hexamethylene diamine, trimethylhexamethylene diamine, isophorone diamine, octamentethylene diamine, dodecamethylene diamine and adipic acid, pimelic acid, suberic acid,fuginic acid, sebacic acid, dodecane dicarboxylic acid, and corresponding ones, can also be prepared b) copolyamides,
  • the homo- or copolyamides of laurolactam are preferably used.
  • Polyesters for example polybutylene terephthalate, and polyether esters, for. B. constructed from terephthalic acid, 1,4-butanediol and poly (oxytetramethylene) glycol.
  • the plastics can contain other additives, such as flame retardants, antistatic agents, plasticizers, lubricants, pigments, dyes, fillers, reinforcing materials or additional stabilizers, such as, for. B. further light stabilizers, antioxidants or heat stabilizers can be added.
  • additives such as flame retardants, antistatic agents, plasticizers, lubricants, pigments, dyes, fillers, reinforcing materials or additional stabilizers, such as, for. B. further light stabilizers, antioxidants or heat stabilizers can be added.
  • alkali metal salts of hypophosphorous acid in particular the sodium salts, in quantities of 0.01 to 1.5, preferably 0.05 to 0.75 and in particular 0.1 to 0.3% by weight. %, based on the plastic.
  • the stabilizing agents according to the invention can be added to the plastics in a known manner. For example, they can be added to the monomers before or during the polymerization or polycondensation, or they can be kneaded into the molding compositions in kneaders or extrusion presses. But you can also add solutions to the plastics, from which, after removing the solvent, for. B. powder for coating agents or foils.
  • the type of incorporation depends in the usual way on the type of plastic, its production or its processing.
  • they can be introduced into the molding compositions during the production of the moldings or - if particularly desired - on the moldings in a suitable manner, for. B. by tumbling or spraying in the form of a solution.
  • the stabilizing agents for plastics which are used for the production of fibers, foils, plates or other extruded or injection molded articles.
  • the molded or unshaped plastics can also be used in the form of latices; they can also be used to manufacture foams.
  • Plastics containing the claimed compounds in amounts that have a stabilizing effect are particularly suitable for the production of moldings which, even when exposed to land for a long time, especially outdoors, must not lose their good mechanical properties and advantageous appearance.
  • Examples 1 and 2 the preparation of the stabilizing agent is described as an example.
  • the physical properties such as volatility (determined by thermogravimetry), solubility in water and petrol, and extractability using solvents such as methanol and toluene (Table 1).
  • the stabilizers produced analogously to Examples 1 or 2 are designated a to k there.
  • Table 2 lists the corresponding properties of the comparison substances, the stabilizers A and B being obtained analogously to DE-A-19 29 921, the stabilizer C according to DE-B-26 06 026 and the stabilizer D according to DE-A-26 38 855 has been.
  • the products to be tested were tumbled onto polyamide 12 granules and the mixture obtained was homogenized in a twin-screw extruder.
  • the granules obtained in this way were then pressed into 1 mm thick plates and exposed to radiation which had been adjusted to the sunlight by means of filters (apparatus equipped with Ultravitalux lamps (no xenon burners).
  • the test was carried out on cut off, approximately 1 ⁇ 3 cm large plates by removing them were bent in the direction of the unirradiated side by 180 ° ("kink test"). The time until the platelets broke was noted.
  • Epoxidized butadiene polymers with different oxygen contents (e.g. 6% epoxy oxygen content according to DIN 16 945) are produced analogously to the above regulation.
  • epoxidized 1,3-butadiene polymer with an epoxy oxygen content of 8.15% (according to DIN 16 945) are mixed with 290 parts by weight of 4-amino-2.2.6.6-tetramethyl-piperidine under nitrogen and implemented with stirring at 190 ° C. After 20 hours, the amine is converted practically quantitatively.
  • the product contains 0.270 m tetramethylpiperidine / 100 g adduct and less than 0.5% by weight of residual epoxide oxygen.
  • Stabilizer (a) was incorporated into a polyether ester together with 0.5% N.N'-bis- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyl] hexamethylene diamine.
  • the breakdown of the polyether esters was higher here, although the stabilizer contained more than twice as much free radical scavenger (290 ppm) as the polyether esters (132 ppm) equipped with the products according to the invention.
  • the low-molecular comparative stabilizer (A) is easily extractable and sublimable. When added to the starting compounds, it was lost to about 90% even under the polycondensation conditions 5 h / 230 ° / 1 mbar.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Claims (5)

1. L'utilisation, comme stabilisant pour des matières synthétiques moulées ou non, d'un produit de polymérisation du butadiène portant des groupes amine et constitué à 70 % par du 1,3-butadiène, ce produit de polymérisation du butadiène ayant été obtenu en faisant réagir un polybutadiène époxydé, d'une teneur en époxyde de 2 à 10 % en masse d'oxygène (selon DIN 16 945), sur une pipéridine substituée de la formule générale:
Figure imgb0010
dans laquelle R représente des radicaux alkyle identiques ou différents comportant de 1 à 3 atomes de carbone, jusqu'à une teneur de 0,3 mole de tétra-alkyl-pipéridine par 100 g de produit de réaction, le polybutadiène de base possédant un poids moléculaire (Mn) de 500 à 6 000, un indice d'iode d'au moins 200 (g d'iode par 100 g) et une teneur en doubles liaisons dans la structure trans de 40 % au plus, ce dans des quantites de 0,01 à 2,0 % en masse, relativement à la matière synthétique.
2. L'utilisation du stabilisant selon la revendication 1,
caractérisée par le fait que le polybutadiène de base possède un poids moléculaire (Mn) de 1 000 à 3 000 et une teneur en cis de 70 à 80 % des doubles liaisons présentes.
3. L'utilisation du stabilisant selon les revendications 1 et 2,
caractérisé par le fait qu'après la réaction sur le dérivé de pipéridine, les doubles liaisons du polybutadiène de base sont hydrogénées jusqu'à présenter un indice d'iode au plus égal à 10 (g d'iode par 100 g).
4. L'utilisation du stabilisant selon les revendications 1 à 3, comme agent de stabilisation pour des matières synthétiques moulées ou non-moulées renfermant des groupes ester et/ou carboxylamide.
5. L'utilisation d'un stabilisant selon la revendication 4,
caractérisé par le fait qu'on utilise conjointement, comme costabilisants, de 0,1 à 1,5 % en masse, relativement à la matière synthétique, de sels alcalins de l'acide hypophosphoreux.
EP83106914A 1982-09-14 1983-07-14 Utilisation d'un polymère de 1,3-butadiène à bas poids moléculaire contenant des groupes amine comme stabilisant de matières plastiques Expired EP0103106B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT83106914T ATE25996T1 (de) 1982-09-14 1983-07-14 Verwendung eines aminogruppen tragenden, niedermolekularen 1,3-butadienpolymerisates als stabilisierungsmittel fuer kunststoffe.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3233949 1982-09-14
DE19823233949 DE3233949A1 (de) 1982-09-14 1982-09-14 Verwendung eines aminogruppen tragenden, niedermolekularen 1,3-butadienpolymerisates als stabilisierungsmittel fuer kunststoffe

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EP0103106A1 EP0103106A1 (fr) 1984-03-21
EP0103106B1 true EP0103106B1 (fr) 1987-03-18

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US (1) US4469829A (fr)
EP (1) EP0103106B1 (fr)
JP (1) JPS6025459B2 (fr)
AT (1) ATE25996T1 (fr)
DE (2) DE3233949A1 (fr)

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DE3706017A1 (de) * 1987-02-25 1988-09-08 Basf Ag Mit funktionalisierten polymeren schlagzaeh modifizierte thermoplaste und deren verwendung zur herstellung von formteilen
US5213897A (en) * 1991-04-03 1993-05-25 Elf Atochem North America, Inc. Epoxy resins containing bound light stabilizing groups
DE4228160A1 (de) * 1992-08-25 1994-03-03 Basf Ag Polymerisate auf Basis von konjugierten Dienen
US5393843A (en) * 1992-08-31 1995-02-28 Shell Oil Company Butadiene polymers having terminal functional groups
US5378761A (en) * 1993-06-24 1995-01-03 Shell Oil Company Monohydroxylated 1,3-polybutadiene/polyisocyanate product reacted with hydroxyl-functional resin
US5554691A (en) * 1993-07-12 1996-09-10 Shell Oil Company Adhesives, sealants, coatings and polymer compositions containing monohydroxylated polydienes in hydroxyl functional resins
US5391637A (en) * 1993-11-23 1995-02-21 Shell Oil Company Capping of anionic polymers with oxetanes
US6835428B1 (en) 1999-03-17 2004-12-28 Cooper Technology Services, Llc Plastic powder filled epoxy paint for tubing
EP1409576A1 (fr) * 2001-06-14 2004-04-21 Basf Corporation Polymeres photostabilises comprenant des fragments photostabilisants, articles qu'ils permettent de realiser et un procede permettant leur realisation
US6806319B2 (en) * 2001-08-08 2004-10-19 Basell Polioelfine Italia S.P.A. Retarding the thermal degradation of polymers using unsaturated aliphatic compounds
DE10330379A1 (de) * 2003-07-04 2005-01-20 Thüringisches Institut für Textil- und Kunststoff-Forschung e.V. Verfahren zur Herstellung von aus der Schmelze verformbaren Polymeren mit verbesserten lichtstabilen thermooxidativen, antibakteriellen, hydrophoben und/oder hydrophilen Eigenschaften
EP1918307A3 (fr) * 2006-10-30 2010-01-20 The Yokohama Rubber Co., Ltd. Élastomère thermoplastique et composition à élastomère thermoplastique
JP6697685B2 (ja) 2017-02-06 2020-05-27 トヨタ自動車株式会社 密閉型電池および組電池

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US2510777A (en) * 1946-12-30 1950-06-06 Du Pont Polyamide treated with a hypophosphorous acid compound
US3595829A (en) * 1968-03-11 1971-07-27 Ici Ltd Polyamides
US3684765A (en) * 1970-01-08 1972-08-15 Sankyo Co Stabilization of synthetic polymers
US3661874A (en) * 1970-06-05 1972-05-09 Minnesota Mining & Mfg Composition of matter
US3945953A (en) * 1972-04-21 1976-03-23 Ciba-Geigy Corporation ω,ω'-Bis-[4-amino-3-aminomethyl-piperidyl-(1)]-alkanes, process for their manufacture and their use
DE2748362A1 (de) * 1977-10-28 1979-05-03 Hoechst Ag Polymere substituierter piperidine, ihre herstellung und verwendung
DE2838930C2 (de) * 1978-09-07 1980-07-03 Chemische Werke Huels Ag, 4370 Marl Wäßriges Behandlungsmittel für Holz und Holzwerkstoffe und dessen Verwendung
SU810737A1 (ru) * 1979-05-04 1981-03-07 Ярославский Политехнический Инсти-Тут Вулканизуема полимерна композици

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Publication number Publication date
ATE25996T1 (de) 1987-04-15
US4469829A (en) 1984-09-04
EP0103106A1 (fr) 1984-03-21
JPS5966457A (ja) 1984-04-14
JPS6025459B2 (ja) 1985-06-18
DE3370347D1 (en) 1987-04-23
DE3233949A1 (de) 1984-03-22

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